Vacuum film-forming apparatus

ABSTRACT

A vacuum film-forming apparatus comprising substrate stages; vacuum chamber-forming containers opposed to the stages; a means for moving the substrate between the stages; and gas-introduction means connected to every containers, wherein one of the stage and the container is ascended or descended towards the other to bring the upper face of the stage and the opening of the container into contact with one another so that vacuum chambers can be formed and that a raw gas and/or a reactant gas can be introduced into each space of the chamber through each gas-introduction means to carry out either the adsorption or reaction step for allowing the raw gas to react with the reactant gas. The apparatus permits the independent establishment of process conditions for the adsorption and reaction processes and the better acceleration of the reaction between raw and reactant gases to give a film having excellent quality and the apparatus can be manufactured at a low cost.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to a vacuum film-forming apparatus ordevice, in particular, to a vacuum film-forming apparatus (an atomiclayer deposition apparatus), which forms a thin film according to theALD technique (Atomic Layer Deposition Technique).

2. Description of the Prior Art

Recently, the patterns of semiconductor integrated circuits haveincreasingly been finer and it has correspondingly been devised thatfine contact holes, trenches and other similar structures having highaspect ratios have been filled up with a distributing wire material suchas Cu and/or Al. If the aspect ratio increases in this manner, it wouldbe difficult to fill up such holes and/or trenches with a conductivefilm in a good or high coverage.

When using, for instance, Cu as a principal distributing wire materialin the case of the foregoing embedded distributing wire structure,deposited Cu may easily diffuse into the neighboring insulating film andthis becomes a cause of various defects and troubles. For this reason, aconductive barrier film is formed between an insulating film and such aconductive film to thus inhibit or control any possible diffusion of Cu.There have been proposed various methods for forming such a barrier filmand there has been known, for instance, a method which comprises thestep of forming a barrier film by depositing a layer of a material suchas Ta, TiN, and/or TaN while using, for instance, the ALD technique(see, for instance, Japanese Un-Examined Patent Publication 2004-6856(see, for instance, claims)).

The ALD technique is similar to the CVD technique in that it makes useof a chemical reaction between precursors. However, they differ from oneanother in that the usual CVD technique makes use of such a phenomenonthat two kinds of gaseous precursors are brought into contact with oneanother to thus cause the reaction between them, while the ALD techniquemakes use of a surface reaction between two precursors. Morespecifically, the ALD technique comprises the steps of forming a desiredmetal film by supplying one of two precursors (for instance, a reactantgas) onto the surface of a substrate on which the other precursor (forinstance, a raw gas) has been adsorbed to bring these precursors intocontact with one another on the substrate surface and to thus cause afilm-forming reaction between them. In this case, the precursorpreliminarily adsorbed on the substrate surface undergoes the reactionwith the precursor subsequently supplied to the surface at a quite highreaction rate on the substrate surface. In this respect, such precursorsmay be in the form of, for instance, solids, liquids or gases and theraw gas is supplied together with a carrier gas such as N₂ or Ar. As hasbeen described above, the ALD technique is a film-forming method whichcomprises alternatively repeating a step of adsorbing a raw gas on asubstrate surface and a step of allowing the adsorbed raw gas to reactwith a reactant gas to thus form a film in an atomic level. Morespecifically, these precursors always undergo such adsorption andreaction within a superficial moving region and accordingly, thistechnique would ensure the considerably high step-coveragecharacteristics. In addition, the raw gas is allowed to react with thereactant gas while separately supplying these gases and therefore, itcan improve the film density. For this reason, this technique hasattracted special interest recently.

A conventional atomic layer-depositing apparatus (ALD apparatus) inwhich a thin film is formed according to the foregoing ALD techniquecomprises a film-forming unit or chamber provided with an evacuationmeans and it further comprises a stage for supporting a substrate(hereunder referred to as “substrate stage”), which is equipped with aheating means and disposed within the film-forming chamber, and agas-introduction means disposed on the side opposite to the substratestage and arranged on the ceiling of the film-forming chamber. As suchan ALD apparatus, there has been known, for instance, one which is sodesigned that a thin film having a desired thickness can be prepared byseparately and periodically supplying a desired raw gas and a desiredreactant gas into the apparatus through a gas-introduction means to thusrepeat a raw gas-adsorption step and a plasma-assisted reaction step forallowing the raw gas to react with the reactant gas by the aid of theplasma (see, for instance, Japanese Un-Examined Patent Publication2003-318174 (see, for instance, claims)).

More specifically, it has been known that when forming a ZrB₂ film as abarrier layer using Zr(BH₄)₄ as such a raw material, such a barrier filmcan be formed according to the following reaction equations (1) and (2):

Zr(BH₄)₄→ZrB₂+B₂H₆+5H₂  (1)

Zr(BH₄)₄+H₂→ZrB₂+B₂H₆+6H₂  (2)

The foregoing reaction equation (1) corresponds to a method in which aZrB₂ film is formed on a substrate by directly and thermally decomposinga raw material using only the thermal assist of the Si substrate heatedby an appropriate means and in this case, an excellent ZrB₂ film can beformed only when the substrate is heated to a high temperature on theorder of not less than 550° C. On the other hand, the foregoing reactionequation (1) corresponds to a method in which hydrogen radicals areadded to a raw material, a reaction of the raw material is induced bythe hydrogen radical and the thermal assist of the Si substrate at arelatively low temperature (on the order of 300 to 350° C.) to thus forma ZrB₂ film on the substrate. In this case, the addition of the hydrogenradical would permit the reduction of the substrate temperature or thereaction temperature required for forming a desired thin film. As anexample of such a method, there has been reported one which comprisesthe steps of forming a ZrB₂ film on a substrate, as a barrier film, atsuch a low temperature of about 300° C. while making use of the remoteplasma CVD technique (see, for instance, J. Appl. Phys., Vol. 91, No. 6,March 2002, pp. 3904-3907 (see, for instance, p. 3904).

Incidentally, to form a thin film by repeating the formation of amono-atomic layer by the ALD technique over desired times, it is quitedesirable that the process conditions such as substrate temperature canseparately and independently be set or established in the foregoingadsorption and reaction steps. However, the foregoing conventionaltechnique never permits the separate and independent setting of suchprocess conditions, but simply the raw and reactant gases can separatelyand periodically be fed to the substrate and accordingly, i.e. there isa time lag between a raw gas introduction and a reactant gasintroduction, and a thin film is formed by repeatedly depositing a layerhaving a thickness of several atoms.

In this connection, if an ALD apparatus is so designed that it comprisesa conveying chamber equipped with an evacuation means and a plurality ofprocessing chambers are arranged around the conveying chamber so that asubstrate can freely be transferred between the neighboring processingchambers by the action of the substrate-conveying means disposed withinthe conveying chamber, the foregoing adsorption and reaction steps mayseparately and independently be conducted. In this method, however, asubstrate is moved between the neighboring processing chambers afteronce transferring the substrate to a conveying chamber. Accordingly,this suffers from such problems that it takes a long period of time forthe transfer of the substrate and that this in turn makes, impossible,the reduction of the cycle time for the formation of desired thin films.Furthermore, it would be necessary for this technique to dispose aconveying chamber, and an evacuation means and a vacuum indicator foreach processing chamber and this accordingly makes the structure of theapparatus complicated and considerably increases the cost required forthe manufacture of the same.

In addition, the film-forming temperature is extremely high in themethod for forming a ZrB₂ film, as a barrier film, by directly,thermally decomposing a raw material while making use of the reactionaccording to the reaction equation (1) and therefore, this method wouldbe accompanied by the foregoing drawbacks or troubles in the case ofdistributing wire layers of semiconductor devices in which Cu and/or Alare used as materials for the distributing wires.

Moreover, the method for forming a barrier film while making use of thereaction according to the reaction equation (2) can reduce thefilm-forming temperature to a level lower than that used in the reactionequation (1), but any film of, for instance, a ZrB₂ film cannot beformed in fine holes having a high aspect ratio in a high coverage. Inthis case, the principal reaction is a gaseous phase reaction betweenZr(BH₄)₄ and hydrogen radicals and therefore, this technique suffersfrom a problem in that an overhang of a ZrB₂ film is formed on the upperportion of each hole or trench and in the worst case, the upper portionof each hole or trench is completely clogged.

DISCLOSURE OF THE INVENTION

Accordingly, it is an object of the present invention, in a broad sense,to solve the foregoing problems associated with the conventionaltechniques and more specifically to provide a vacuum film-formingapparatus which permits the separate and independent establishment ofthe processing conditions for adsorption and reaction steps and permitsthe formation of a thin film having excellent quality by theacceleration of the reaction between a raw gas and a reactant gas; whichis so designed that it can improve or reduce the cycle time of thefilm-forming process; and which can be manufactured at a lower cost. Inthe case of forming a thin film on a substrate by using the foregoingapparatus, it is possible to form a thin film on the inner walls of, forinstance, fine holes and/or trenches in a good coverage without beingaccompanied by the formation of any overhang on the upper portion ofthese holes and trenches.

According to an aspect of the present invention, there is provided avacuum film-forming apparatus as an ALD apparatus, the apparatus beingcharacterized in that it comprises a plurality of substrate stages forplacing a subject (hereunder referred to as “substrate(s)”) on which adesired film is deposited and capable of freely moving up and down; aplurality of containers, each serving as a vacuum chamber (hereunderreferred to as “vacuum chamber-forming container(s)”), which arearranged in such a manner that they are opposed to the plurality ofsubstrate stages and which can freely move up and down; a conveyingmeans for moving the substrate between the plurality of substratestages; and a plurality of gas-introduction means which are separatelyconnected to every corresponding vacuum chamber-forming containers,wherein the apparatus is so designed that, upon practicing thefilm-forming process, one of the substrate stage and the vacuumchamber-forming container is ascended or descended towards the other orboth of them are simultaneously ascended or descended to thus bring theupper face of the substrate stage and the opening of the vacuumchamber-forming container into contact with one another so that eachcorresponding vacuum chamber can be formed, which is surrounded by eachcorresponding pair comprising the substrate stage and the vacuumchamber-forming container and that a desired raw gas and/or a reactantgas can be introduced into every spaces of the plurality of the vacuumchambers thus formed through the gas-introduction means to thus carryout therein either the adsorption step in which the raw gas is adsorbedon the substrate or the reaction step for allowing the adsorbed raw gasto react with the reactant gas.

More specifically, the foregoing film-forming apparatus is so designedthat after placing a substrate on the substrate stage and forming thecorresponding vacuum chamber from the substrate stage and the vacuumchamber-forming container, a desired raw gas is introduced into thespace thus formed through the gas-introduction means to thus carry outan adsorption step in which the raw gas is adsorbed on the surface ofthe substrate; that after the space is then opened, the substratecarrying the raw gas adsorbed on the surface thereof is transferred toanother substrate stage by the action of the conveying means; that afterforming a vacuum chamber from the another substrate stage and anothervacuum chamber-forming container, a desired reactant gas is introducedinto the resulting space through the gas-introduction means to thuscarry out a reaction step in which the adsorbed raw gas is allowed toreacted with the reactant gas introduced; and that a series of theforegoing adsorption and reaction steps are repeated over apredetermined times to thus form a thin film having a desired thickness.

In this case, the film-forming apparatus is likewise so designed as tosimultaneously form a plurality of vacuum chambers and spaces, in whicheither an adsorption step or a reaction step can be conducted, withinthe apparatus and accordingly, the use of this apparatus would permitthe separate and independent establishment of the process conditions forcarrying out the adsorption and reaction steps for the furtherimprovement or acceleration of the reaction and this in turn permit theformation of a thin film having high quality. Moreover, it is notnecessary to separately dispose a conveying chamber for transferring awafer (or a substrate) during the film-forming process. This wouldpermit the substantial reduction of the time required for conveying asubstrate on which a desired thin film is deposited and as a result,this in turn reduces the cycle time of the film-forming process and thusthe apparatus can be manufactured at a low cost.

According to a preferred embodiment, the apparatus further comprises aunit for generating plasma (a plasma generator) which is positioned atthe exterior of at least one of the foregoing vacuum chamber-formingcontainer. If a plasma generator is provided at least for each spacewherein an adsorption step is carried out among other spaces, thesurface of the substrate and the inner wall surfaces of the spaces canbe purified by the irradiation thereof with the plasma thus generatedand accordingly, any impurity possibly present thereon can substantiallybe removed, prior to, for instance, the adsorption of a raw gas onto thesubstrate surface. In this respect, such a plasma generator may likewisebe provided for each space for carrying out a reaction step. In thiscase, the plasma generator may serve to activate a reactant gas to thusaccelerate the desired reaction.

According to another embodiment, the film-forming apparatus ischaracterized in that a catalytic means is provided, which is connectedto the vacuum chamber-forming container for carrying out a reaction stepand placed on the exterior of the film-forming apparatus or within thevacuum chamber for carrying out a reaction step, so that a reactant gasexcited by the catalytic means can be introduced into the reactionspace. Thus, the apparatus permits the introduction of an excitedreactant gas into the reaction space and therefore, the reaction can beaccelerated to thus give a thin film having excellent quality.

According to a further preferred embodiment of the film-formingapparatus, the foregoing catalytic means and the vacuum chamber-formingcontainer in which the reaction step is carried out are equipped withcooling means. Such cooling means would permit the inhibition or controlof any excessive increase in the temperature within the reaction spaceincluding the substrate due to the heat generated by, for instance, acatalyst such as a tungsten wire.

According to still another preferred embodiment, the apparatus ischaracterized in that the dimensions of the opening of the vacuumchamber-forming container and the substrate stage are so designed that agap having a desired size can be formed between the inner peripheralface of the opening and the outer peripheral face of the substrate stagewhen practicing the adsorption and/or reaction steps in the spacesestablished within the vacuum chamber and that the exhaust gas can bedischarged from the apparatus through the gap. If the apparatus has sucha structure capable of forming such a gap, the pressure in the space maybe maintained at a desired level when introducing a desired gas into thespace. In this case, the size of the gap may be changed to control theconductance.

According to a further preferred embodiment of the foregoing apparatus,the vacuum chamber-forming container is so designed that it has abell-jar shape.

According to a still further preferred embodiment of the foregoingapparatus, each of the foregoing plurality of substrate stages isequipped with a means for heating a substrate on which a desired film isdeposited. If each substrate stage is thus provided with such a heatingmeans, the substrate placed on the stage can separately be heated to atemperature suitable for carrying out each of the adsorption andreaction steps.

According to another aspect of the present invention, there is alsoprovided a vacuum film-forming apparatus as an ALD apparatus, theapparatus being characterized in that it comprises a turn table forplacing and transferring a substrate on which a desired film isdeposited and capable of freely moving up and down; a plurality ofvacuum chamber-forming containers, which are arranged in such a mannerthat they are opposed to the turn table and which can freely move up anddown; and a plurality of gas-introduction means which are separatelyconnected to every corresponding vacuum chamber-forming containers,wherein the apparatus is so designed that upon practicing thefilm-forming process, one of the turn table and the vacuumchamber-forming container is ascended or descended towards the other orboth of them are simultaneously ascended or descended to thus bring theupper face of the turn table and the opening of the vacuumchamber-forming container into contact with one another so that aplurality of vacuum chambers can be formed, each of which is surroundedby a part of the turn table and each corresponding vacuumchamber-forming container and that a desired raw gas and/or a desiredreactant gas can be introduced into every spaces of the plurality of thevacuum chambers thus formed through the gas-introduction means to thuscarry out therein either the adsorption step in which the raw gas isadsorbed on the surface of the substrate or the reaction step forallowing the adsorbed raw gas to react with the reactant gas.

In this case, the turn table for placing the substrate also functions asa means for conveying the substrate and therefore, the turn table wouldpermit the simultaneous transfer of a plurality of substrates. Inaddition, when the turn table is so designed that it can rotate only inone direction, the adsorption and reaction steps can, in order, beconducted by conveying the substrates synchronous with the rotation ofthe turn table.

Incidentally, when simultaneously carrying out the adsorption andreaction steps for a plurality of substrates, it is sufficient that aplurality of vacuum chambers can simultaneously be formed byappropriately controlling the movement of the turn table and the vacuumchamber-forming containers.

According to a preferred embodiment of the foregoing apparatus, the turntable is provided with, on the same circumference of a circle, aplurality of trough holes the number of which is identical to that ofthe vacuum chamber-forming containers; a member for supporting eachsubstrate is disposed at the periphery of each though hole; and theapparatus is provided with a substrate stage, as a means for ascendingand descending the substrate placed thereon, which can freely go up anddown and which can pass through the hole. This substrate stage alsotakes part in the formation of a vacuum chamber together with the turntable and vacuum chamber-forming container upon the practice of theprocess.

According to another preferred embodiment of the foregoing apparatus,the apparatus further comprises a unit for generating plasma which ispositioned at the exterior of at least one of the foregoing vacuumchamber-forming container. If the unit for generating plasma is providedat least for each space wherein an adsorption step is carried out amongother spaces, the surface of the substrate and the inner wall surfacesof the spaces can be purified by the irradiation thereof with the plasmathus generated and accordingly, any impurity possibly present thereoncan substantially be removed, prior to, for instance, the adsorption ofa raw gas onto the substrate surface. In this respect, such aplasma-generating unit may likewise be disposed in each space forcarrying out a reaction step. In this case, the plasma-generating unitmay serve to activate a reactant gas to thus accelerate the desiredreaction.

According to still another embodiment of the film-forming apparatus, itis characterized in that a catalytic means is provided, which isconnected to the vacuum chamber for carrying out a reaction step andplaced on the exterior of the film-forming apparatus or within thevacuum chamber for carrying out a reaction step so that a reactant gasexcited by the catalytic means can be introduced into the reactionspace. Thus, the apparatus permits the introduction of an excitedreactant gas into the reaction space and therefore, the reaction can beaccelerated to thus give a thin film having excellent quality.

According to a further preferred embodiment of the film-formingapparatus, the foregoing catalytic means and the vacuum chamber-formingcontainer in which the reaction step is carried out are equipped with acooling means. Such a cooling means would permit the inhibition orcontrol of any excessive increase in the temperature within the reactionspace including the substrate due to the heat generated by, forinstance, a catalyst such as a tungsten wire.

According to a still further preferred embodiment of the film-formingapparatus, the apparatus is characterized in that a plurality of exhaustports are provided in the vicinity of the external periphery of thesubstrate-supporting member. If the apparatus is provided with suchexhaust ports so that the film-forming apparatus can externally beexhausted, the pressure of the space can be maintained at a desiredlevel when introducing a desired gas into the space. In this case, theconductance of the apparatus can be adjusted by arbitrarily varying thesize of each exhaust port.

According to a further preferred embodiment of the foregoing apparatus,the vacuum chamber-forming container is one having a bell-jar shape.

According to a still further preferred embodiment of the foregoingapparatus, each of the foregoing plurality of substrate stages isequipped with a means for heating a substrate on which a desired film isdeposited. If each substrate stage is thus provided with such a heatingmeans, the substrate placed on the stage can separately be heated to atemperature suitable for carrying out each of the adsorption andreaction steps.

According to a further preferred embodiment of the film-formingapparatus, the apparatus is further provided with a stage-supportingtable, in the interior of which is provided with an exhaust passage orpath, for placing the substrate stage. The use of such an exhaust meanswould permit the prevention of the formation of any particle due to agas-phase reaction caused by mixing of a raw gas and reactant gas withinthe film-forming apparatus.

As has been described above in detail, the vacuum film-forming apparatusaccording to the present invention permits the independent establishmentof the process conditions for adsorption and reaction steps, theacceleration of the reaction between a raw gas and a reactant gas andthe formation of a thin film having more excellent film quality.Moreover, the apparatus likewise permits the considerable reduction ofthe cycle time of film-forming processes and the apparatus can bemanufactured at a low cost.

Moreover, the thin vacuum film-forming apparatus according to thepresent invention permits the practice of adsorption and reaction stepsat a low temperature according to the ALD technique and the apparatuswould permit, for instance, the formation of a thin film even on theinner walls of fine holes and/or trenches having a high aspect ratio ina high coverage without causing any overhanging phenomenon at the upperportions of, for instance, these fine holes and/or trenches.

BRIEF DESCRIPTION OF THE DRAWINGS

The present invention will hereunder be described in more detail withreference to the accompanying drawings, wherein

FIG. 1 shows a schematic block diagram for illustrating an embodiment ofthe vacuum film-forming apparatus according to the present invention andmore specifically, wherein (a) is a diagram showing the structure of theapparatus observed during the step of conveying a substrate on which afilm is formed; (b) is a diagram showing the structure of the apparatusobserved during the film-forming step and (c) is a top plan viewobserved from the direction A-A specified in FIG. 1( a);

FIG. 2 is a schematic diagram for illustrating an example of thecatalytic means used in the present invention;

FIG. 3 is a schematic diagram for illustrating another embodiment of thevacuum film-forming apparatus according to the present invention;

FIG. 4 is a top plan view of the vacuum film-forming apparatus as shownin FIG. 3 from which the bell-jar shaped container is removed;

FIG. 5 is a block diagram for explaining the method for conveying asubstrate on which a film is formed when a thin film is formed using thevacuum film-forming apparatus as shown in FIG. 3 or 4 and this is across sectional view taken along the line B-B specified in FIG. 4,wherein (a) corresponds to a schematic side view of the apparatusobserved during the step of conveying the substrate; (b) corresponds toa schematic side view of the apparatus observed when a vacuum chamber isformed; and (c) corresponds to a schematic side view of the apparatusobserved when the film-forming process is put into practice;

FIG. 6 is a schematic block diagram for illustrating the method forgenerating a raw gas when using the vacuum film-forming apparatusaccording to the present invention, wherein (a) is a diagram forexplaining an example of the means for generating the raw gas; (b) is adiagram for explaining an example of another means for generating theraw gas; and (c) is a diagram for explaining an example of still anothermeans for generating the raw gas.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

First of all, an embodiment of the vacuum film-forming apparatus (anatomic layer deposition apparatus (ALD apparatus)) according to thepresent invention will be described below in detail while referring toFIGS. 1( a) to (c) attached hereto. In FIG. 1, (a) is a cross sectionalview schematically showing the structure of the apparatus observedduring the step of conveying a subject on which a film is formed or asubstrate; (b) is a cross sectional view schematically showing thestructure of the apparatus observed when putting the film-forming stepinto practice; and (c) is a top plan view observed from the directionA-A specified in FIG. 1( a).

The vacuum film-forming apparatus 101 as shown in FIG. 1 is connected toan evacuation means (not shown) such as a turbo-type molecular pump or arotary pump such that any suitable degree of vacuum (for instance,1×10⁻⁶ Torr) can be established in the interior of the film-formingapparatus. A plurality of substrate stages 102 a and 102 b (theapparatus shown in FIG. 1 is provided with two such substrate stages)each capable of receiving a substrate S on which a thin film is formedare disposed in the vacuum film-forming apparatus 101 and each of thesesubstrate stages 102 a and 102 b is so designed that it can freelyascend and descend by the action of a driving means 103 a and 103 b suchas a motor or an air cylinder.

Each of these substrate stages 102 a and 102 b is provided with abuilt-in heating means (not shown) such as a resistance heater and thuseach substrate stage can heat substrate S to a desired temperature.Moreover, in the vacuum film-forming apparatus 101, bell-jar shapedvacuum chamber-forming containers 104 a and 104 b are arranged in such amanner that they are opposite to every corresponding substrate stages102 a and 102 b so that each pair of the substrate stage and thebell-jar shaped vacuum chamber-forming container can form eachcorresponding vacuum chamber (the apparatus as shown in FIG. 1 includestwo vacuum chambers) when putting the film-forming process intopractice. For instance, when ascending the substrate stage 102 a or 102b, the opening of the corresponding bell-jar shaped vacuumchamber-forming container 104 a or 104 b covers each substrate stage tothus form each corresponding vacuum chamber and each space 105 a or 105b within the vacuum chamber thus formed functions as a chamber forpracticing the film-forming process, in which the adsorption andreaction steps are conducted.

When practicing the foregoing film-forming process, the substrate stages102 a and 102 b are elevated by the operation of the driving means 103 aand 103 b so that the substrates S placed on these substrate stages 102a and 102 b are arranged within the resulting spaces 105 a and 105 b,respectively. In this respect, the dimensions of the openings of thebell-jar shaped containers 104 a and 104 b and those of the crosssection of the substrate stages are so designed that a gap 106 a or 106b having a desired size can be formed between the outer peripheral sidewall of each substrate stage 102 a or 102 b and the inner peripheralface of the opening of each bell-jar shaped container 104 a or 104 b.Thus, when introducing a desired gas into each of spaces 105 a and 105b, the gas can externally be evacuated from the space through each gap106 a or 106 b to thus maintain the pressure within each space 105 a or105 b at a predetermined level (see FIG. 1( b)). In this case, the gasdischarged from the space is externally discharged from the apparatusthrough an exhaust passage V connected to the gap. Regarding thisexhaust passage, each vacuum chamber may separately be provided witheach particular exhaust passage or a plurality of vacuum chambers may beconnected to a common exhaust passage through which the exhaust gas maybe discharged, as will be seen from FIG. 1. In this connection, the sizeof each gap 106 a or 106 b can be changed to control the conductancethereof.

Gas-introduction means 107 a and 107 b having a known structure aredisposed on the ceiling portions of the bell-jar shaped containers 104 aand 104 b in such a manner that they are opposed to the substrates S onwhich a thin film is formed. These gas-introduction means 107 a and 107b are so designed that they are connected to corresponding gas sources(not shown) through pipe lines 108 a and 108 b for gas passage,respectively, and that a desired raw gas can thus be introduced into thespace 105 a of one vacuum chamber to conduct the adsorption step, whilea desired reactant gas can be introduced into the space 105 b of theother vacuum chamber to conduct the reaction step. It is a matter ofcourse that these adsorption and reaction steps can likewise be carriedout by introducing a raw gas into the space 105 b and a reactant gasinto the space 105 a. In this respect, these adsorption and reactionsteps can be carried out in the space of the same vacuum chamber, butthis would be undesirable in that there is a problem of the presence ofresidual gases.

On the other hand, in the case of a vacuum chamber for carrying out theadsorption step, a plasma generator having an RF coil 109 connected to aradiofrequency power source is provided on the outer wall of thecontainer 104 a having a bell-jar shape so that the plasma of, forinstance, argon can be generated in the space 105 a prior to the initialadsorption of a raw gas onto the surface of a substrate S on which afilm is to be formed, in order to make the surface of the substrate Sclean by the irradiation with the plasma or that NF₃ gas can be passedthrough the apparatus while operating the plasma generator to thuspurify the interior of the vacuum chamber.

When carrying out the reaction step while introducing a reactant gasinto the space 105 b, it is desirable that the reaction of the raw gaswith the reactant gas can be accelerated without excessively increasingthe temperature of the substrate S. To this end, for instance, a plasmagenerator having an RF coil (not shown) connected to a radiofrequencypower source may be disposed on the outer wall of the container 104 bhaving a bell-jar shape so that an argon plasma is generated within thespace 105 b to thus carry out a plasma-assisted reaction step.

It is also preferred that the foregoing vacuum film-forming apparatus101 is provided with a means for exciting the reactant gas to beintroduced into the space 105 b for carrying out the reaction step tothus form radicals of the gas. If it is intended to supply, onto thesurface of the substrate S, the reactant gas excited and converted intoradicals, the apparatus may, for instance, be designed as follows: acatalytic means (not shown) such as a tungsten catalyst wire is disposedin a gas piping 108 b connected to a gas-introduction means 107 b tothus supply the excited reactant gas onto the substrate S through thegas-introduction means equipped with a shower plate or a dispersionplate; or the foregoing catalytic means is arranged within the space 105b and on the downstream side of a shower plate or a dispersion plate ofthe gas-introduction means 107 b and the reactant gas to be introducedinto the space is first excited by the action of the catalyst and thensupplied to the substrate S through the shower plate or the dispersionplate.

In the case where the apparatus is provided with the foregoing catalyticmeans, for instance, within the space 105 b, it is preferred that theshower plate or the dispersion plate made of, for instance, quartz oralumina is equipped with a cooling means such as a water-cooling piping.The use of such a cooling means would permit the control of anyundesirable temperature increase in the space due to the heat generatedby the catalytic wire observed when applying an electric current to thecatalytic means. It is preferred that a cooling means may likewise bedisposed on the outer wall of the container 104 b having a bell-jarshape which constitutes the space 105 b, in addition to the place in theproximity to, for instance, the shower plate to thus control thetemperature in the space 105 b.

The foregoing catalytic means will be described below in more detailwith reference to an embodiment of the catalyst means schematicallyshown in FIG. 2. The excited reactant gas is generated within a catalystchamber 202 connected to and communicated with a vacuum chamber througha valve 201. Arranged within the catalyst chamber 202 is, for instance,a wire 203 consisting of a known catalyst metal for excitation such astungsten (W) and a cooling means 204 is attached to the outer wall ofthe catalyst chamber 202. Moreover, the apparatus is likewise sodesigned that an exhaust means 205 consisting of a vacuum pump such as aturbo-type molecular pump is also connected to the catalyst chamber 202and that the catalyst chamber can thus be evacuated to a pressure on theorder of, for instance, 0.1 to 10 Torr (13.3 to 1333.3 Pa). In thisrespect, the reactant gas cannot be excited efficiently at a pressurebeyond the range specified above. In this connection, a vent line 207may be established by arranging a valve 206 between the catalyst chamber202 and the exhaust means 205, the vent line being established betweenthe valve 206 and the catalyst chamber 202. The establishment of such avent line would permit the inhibition of any change of the pressure inthe catalyst chamber by opening or closing a valve 201 such as anisolation valve for dividing the catalyst chamber 202 from the vacuumchamber. The reactant gas is introduced into the catalyst chamber 202through a gas-introduction port 202 a.

A substrate-conveying means 110 is arranged between substrate stages 102a and 102 b as shown in FIG. 1. This substrate-conveying means 110 has ashaft member 110 a which can freely go up and down through the action ofa driving means (not shown) such as a motor or an air cylinder and anarm 110 b, which can freely rotate round the shaft serving as a center,is attached to one end of the shaft member 110 a. The arm 110 b canappropriately be rotated while the shaft member 110 a is ascended ordescended so that a substrate S on which a film is formed can betransferred from the substrate stage 102 a to the substrate stage 102 bor vice versa.

In addition, a substrate-conveying chamber (a road-lock chamber) 111 isconnected to the foregoing vacuum film-forming apparatus 101 through agate valve 112 and the substrate S can thus be transferred from thevacuum film-forming apparatus 101 and the road-lock chamber 111 by theoperation of a substrate-conveying means such as a robot disposed withinthe road-lock chamber.

In FIG. 1, the reference numeral 113 represents an exhaust meansprovided with an exhaust path V.

The foregoing vacuum film-forming apparatus 101 is provided with aseparately formed vacuum chamber having a space 105 a for carrying outan adsorption step and a vacuum chamber having a space 105 b forcarrying out a reaction step. For this reason, process conditions forsuch adsorption and reaction steps can independently be establishedaccording to the method for forming a thin film such as a barrier filmwhile using this vacuum film-forming apparatus and therefore, thereaction between a raw gas and a reactant gas can be accelerated to thusgive a thin film having excellent quality. This further allows thereduction of the time required for the transfer of the substrate S andas a result, the cycle time required for carrying out the film-formingprocess can thus be reduced. Moreover, the apparatus can thus bemanufactured at a low cost.

Then, a vacuum film-forming apparatus according to another embodiment ofthe present invention will be described in detail below with referenceto the accompanying drawings FIGS. 3 to 5. FIG. 3 is a schematic diagramshowing the structure of a vacuum film-forming apparatus in which avacuum chamber formed is surrounded by a turn table and a containerhaving a bell-jar shape. FIG. 4 is a top plan view of the vacuumfilm-forming apparatus as shown in FIG. 3 from which the bell-jar-shapedcontainer is removed. Further FIG. 5 is a schematic block diagram forexplaining a film-forming process for forming a thin film such as abarrier film and this is a cross sectional view taken along the line B-Bspecified in FIG. 4, wherein (a) corresponds to a condition observedduring the step of conveying the substrate on which a film is formed;(b) corresponds to a condition observed when a vacuum chamber is formed;and (c) corresponds to that observed when the film-forming process isput into practice.

The vacuum film-forming apparatus (an ALD apparatus) 301 shown in FIGS.3 to 5 has a structure approximately identical to the vacuumfilm-forming apparatus 101 shown in FIG. 1, but the former is sodesigned that it can simultaneously process a plurality of substrates S(in this case, four substrates are shown) on which a thin film isformed. For the convenience of the drawing up of figures and for makingthe explanation simple, there are shown two vacuum chambers in FIG. 3,four vacuum chambers in FIG. 4 and only one vacuum chamber in FIG. 5.

There are disposed four substrate stages 302 a, 302 b, 302 c and 302 dwithin the vacuum film-forming apparatus 301 equipped with an evacuationmeans, each of these substrate stages is so designed that it can freelygo up and down by the action of a driving shaft 304 a, 304 b, 304 c or304 d of a driving means 303 a, 303 b, 303 c or 303 d such as a motor oran air cylinder, and mounted on and fixed to a stage-supporting table305 also serving as an exhaust means as will be detailed later. In thiscase, these four substrate stages are arranged on the same circumferenceof a circle at equal spaces.

Each substrate stage 302 a to 302 d is equipped with a built-in heatingmeans (not shown) such as a resistance heater and the substrate S canthus be heated to a desired temperature for each substrate stage. Inaddition, the vacuum film-forming apparatus 301 is also provided thereinwith bell-jar-shaped containers 306 a, 306 b, 306 c and 306 d each ofwhich is opposed to each corresponding substrate stage 302 a to 302 d.Each bell-jar-shaped container forms a vacuum chamber upon the practiceof the film-forming process. For instance, when elevating a turn tableas will be described later towards to opening of the bell-jar-shapedcontainer (or when bringing each bell-jar-shaped container down to theturn table), the opening of each bell-jar-shaped container is coveredwith the turn table so that four vacuum chambers can be formed andaccordingly, the space 307 a, 307 b, 307 c or 307 d of each vacuumchamber may function as a film-forming chamber in which the adsorptionand reaction steps are carried out in a predetermined order.

Disposed within the vacuum film-forming apparatus 301 is a turn table308 which also serves as a substrate-conveying means for transportingthe substrate S. The turn table 308 is provided with circular throughholes 308 a, 308 b, 308 c and 308 d arranged on the same circumferenceof a circle at equal spaces and the number of which is identical to thatof the bell-jar-shaped containers so that, in the practice of thefilm-forming process, each substrate stage can pass through eachcorresponding through hole when the stage-supporting table 305 isascended by the operation of each driving shaft 304 a to 304 d capableof freely going up and down and connected to each corresponding drivingmeans 303 a to 303 d. Substrate-supporting members 309 a, 309 b, 309 cand 309 d for holding substrates S, on which a film is formed, aredisposed on the turn table 308 and at least part of the peripheralregion of each through hole. The turn table 308 is likewise so designedthat it can freely be rotated by the action of a driving shaft 308-2connected to a driving means 308-1.

The stage-supporting table 305 may also be freely rotatable.

In this connection, it is preferred that the turn table 308 should beelevated till each opening of the bell-jar-shaped container 306 a to 306d is completely covered with the upper face of the turn table 308. Inthis case, the turn table 308 is provided with a plurality of exhaustholes 308 e, 308 f, 308 g and 308 h for the evacuation of each space 307a to 307 d, which are arranged in the proximity to the outer peripheralwall of each corresponding substrate-supporting member 309 a to 309 d sothat the pressure in each space can be maintained at a desired levelwhen introducing a desired gas into the space. The number of exhaustholes 308 e to 308 h and the area of the opening thereof may be changedso as to control the conductance. In this connection, the upper face ofthe turn table 308 may slightly be separated from the side of theopening of each bell-jar-shaped container 306 a to 306 d. In this case,however, the presence of such an interstice is not preferred from theviewpoint of the control of the conductance since the resultinginterstice may likewise serve as an exhaust when introducing a desiredgas into the space 307 a to 307 d.

As has been described above, each space 307 a to 307 d is evacuatedthrough the exhaust hole 308 e to 308 h formed through the turn table308. At this stage, it is necessary to prevent the formation of anyparticle, which may be formed as a result of the admixture of a raw gasand a reactant gas within the vacuum film-forming apparatus 0301 and dueto the gas-phase reaction taken place between them. To this end, theapparatus is preferably designed as follows: an exhaust path is formedin the stage-supporting table 305 and exhaust ports 305 a, 305 b, 305 cand 305 d are arranged at positions in good agreement with the exhaustholes 308 e to 308 h so that the stage-supporting table also functionsas an exhaust means and that the exhaust holes may communicate with theexhaust ports during the adsorption step or the reaction step (FIG. 5(c)). In this case, the outlet of the exhaust path is connected to thewall face of the vacuum film-forming apparatus 301 through a piping 310such as a bellows type one so that the stage-support member (or theexhaust path) may go up and down in response to the action or movementof the substrate stage 302 a to 302 d. The position of placing thepiping 310 is not particularly restricted, if the gas is uniformlyexhausted out of the apparatus through the exhaust path. The piping 310may be placed as shown in FIG. 3. The conductance is controlledaccording to each film-forming process. These exhaust paths arepreferably so designed that they can be combined into one as shown inFIG. 3 to thus externally discharge gases out of the vacuum film-formingapparatus 301.

Each bell-jar-shaped container 306 a to 306 d is provided, on itsceiling, with a gas-introduction means 311 a, 311 b, 311 c or 311 dwhich is equipped with a shower plate or a dispersion plate having aknown structure and which faces each corresponding substrate S to bedeposited with a film so that a raw gas may be introduced into, forinstance, the bell-jar-shaped containers 306 a and 306 c or a reactantgas may be introduced into, for instance, the bell-jar-shaped containers306 b and 306 d through gas piping works 312 a, 312 b, 312 c and 312 d.In this case, it is also possible to introduce a reactant gas into thebell-jar-shaped containers 306 a and 306 c and a raw gas into thebell-jar-shaped containers 306 b and 306 d. Thus, if the raw gas andreactant gas are introduced in this manner and the turn table 308 isrotated in one direction, the adsorption and reaction steps cancontinuously be carried out while stepwise feeding, in order, thesubstrate S to be deposited with a desired film.

Moreover, each bell-jar-shaped container may be provided, on its outerwall, with a plasma generator having an RF coil 313 connected to aradiofrequency power source, like the bell-jar-shaped container as shownin FIG. 1. The details thereof are the same as those described above inconnection with FIG. 1 and therefore, the description thereof will beomitted herein.

In addition, the vacuum film-forming apparatus 301 is preferablyprovided with a catalytic means as a means for exciting a reactant gasto be introduced into the space for practicing the desired reaction stepand converting the same into radicals, like the vacuum film-formingapparatus 101 as shown in FIG. 1. The details thereof are likewise thesame as those described above in connection with FIG. 1 and therefore,the description thereof will be omitted herein.

Furthermore, a substrate-conveying chamber (a road-lock chamber) 314 isconnected to the vacuum film-forming apparatus 301 through a gate valve315 and the substrate S can thus be transferred from the vacuumfilm-forming apparatus 301 and the road-lock chamber 314 by theoperation of a substrate-conveying means (not shown) such as a robotdisposed within the road-lock chamber.

The foregoing vacuum film-forming apparatus 301 is provided with aseparately formed vacuum chamber having a space for carrying out anadsorption step and a vacuum chamber having a space for carrying out areaction step. For this reason, process conditions for such adsorptionand reaction steps can independently be established according to themethod for forming a thin film such as a barrier film while using thisvacuum film-forming apparatus and therefore, the reaction between a rawgas and a reactant gas can be accelerated to thus give a thin filmhaving excellent quality. This further allows the reduction of the timerequired for the transfer of the substrate S and as a result, the cycletime required for carrying out the film-forming process can thus bereduced. Moreover, the apparatus can thus be manufactured at a low cost.

Then the thin film-forming method, which makes use of the vacuumfilm-forming apparatuses 101 and 301 as shown in FIGS. 1 and 3 to 5,respectively, will be detailed below while taking the method forpreparing a barrier film by way of example.

In forming a thin film using the foregoing vacuum film-forming apparatusaccording to the ALD technique, the method comprises the steps ofplacing a substrate, on which a desired film is deposited, on asubstrate stage or a turn table; then introducing a desired raw gas intothe space within a vacuum chamber formed between the substrate stage orthe turn table and a vacuum chamber-forming container to thus adsorb theraw gas on the surface of the substrate; transferring the substratecarrying the raw gas adsorbed thereon to the space within another vacuumchamber; and then introducing a reactant gas into the space of theanother vacuum chamber to induce the reaction of the adsorbed raw gaswith the reactant gas and to thus form a thin film on the substrate. Themethod having such a construction would permit the independentestablishment of the process conditions for these adsorption andreaction steps, the acceleration of the reaction between the raw gas andthe reactant gas and the formation of a thin film having more excellentfilm quality. Moreover, the method likewise permits the considerablereduction of the cycle time of the film-forming process and also permitsthe formation of a thin film according to a low temperature process.

More particularly, in forming a thin film using the foregoing vacuumfilm-forming apparatus according to the ALD technique, a methodcomprises the steps of arranging a substrate, on which a desired film isdeposited and on which holes and/or trenches are formed, within thespace of a vacuum chamber provided with a raw gas-introduction means;introducing a raw gas into the space under a predetermined pressure tothus adsorb the gas onto the surface of the substrate; transferring thesubstrate carrying the raw gas adsorbed thereon to the space of a vacuumchamber provided with a reactant gas-introduction means; and thenintroducing an excited reactant gas into the space to induce thereaction between the adsorbed raw gas and the excited reactant gas andto thus form a thin film on the substrate including the inner walls ofthe holes and/or trenches. The method having such a construction wouldpermit the independent establishment of the process conditions for theseadsorption and reaction steps, the acceleration of the reaction betweenthe raw gas and the reactant gas and the formation of a thin film havingmore excellent film quality. Moreover, the method likewise permits theconsiderable reduction of the cycle time of the film-forming process andalso permits the formation of a thin film even on the inner walls of theholes and/or trenches in good coverage according to a low temperatureprocess, without being accompanied by any overhanging phenomenon at theupper portions of, for instance, these fine holes and/or trenches.

In the thin film-forming method carried out using the vacuumfilm-forming apparatus 101 as shown in FIG. 1, the vacuum film-formingapparatus is first operated to evacuate the interiors of the road-lockchamber 111 and the vacuum film-forming apparatus 101, a substrate S tobe deposited with a desired film is conveyed from the road-lock chamber111 to the interior of the vacuum film-forming apparatus 101 and thenplaced on the substrate stage 102 a. At this stage, the heating meansbuilt in each substrate stage 102 a (102 b) is also operated.

When the pressure in the vacuum film-forming apparatus 101 reaches adesired value (the order of, for instance, 2×10⁻⁵ Torr) due to theevacuation, the substrate stage 102 a is ascended such that thesubstrate stage and the bell-jar shaped container 104 a can form a space105 a (or a vacuum chamber) and that the substrate S is positionedwithin the space (see FIG. 1( b)). At this stage, it is preferred thatthe substrate stage 102 b is simultaneously ascended such that theatmosphere within the space 105 b thus formed is isolated from thatwithin the space 105 a. In this case, the bell-jar-shaped container maybe descended so that the container and the substrate stage may form aspace or the substrate stage and the bell-jar-shaped container mayrelatively be ascended or descended to thus form a desired space or avacuum chamber. The vacuum chambers as will be described below can beformed according to the same manner.

In the state in which the substrate S to be deposited with a film isplaced in the position as shown in FIG. 1( b), the temperature of thesubstrate S on the substrate stage 102 a is maintained at apredetermined level (at a temperature ranging from 50 to 450° C. andpreferably 80 to 300° C., for instance, 150° C.) by using a heatingmeans, while a raw gas such as Zr(BH₄)₄ gas (0.5 to 200 sccm) isintroduced into the vacuum chamber through the gas-introduction means107 a in such a manner that the pressure within the space 105 a formedin the vacuum chamber is maintained at a desired level (on the order of,for instance, 3×10⁻¹ Torr) and then the foregoing conditions aremaintained for a predetermined period of time (0.1 to 10 seconds, forinstance, 2 seconds) to thus adsorb the raw gas onto the substrate S.

If the temperature of the substrate S is less than 50° C., it takes avery long time for the completion of the desired process, while if itexceeds 450° C., any barrier layer (a layer of, for instance, a ZrB₂film or a ZrBN film) cannot be used for a distributing wire layer for asemiconductor device which makes use of Cu and/or Al. In the adsorptionstep, if the raw gas-supply time is less than 0.1 second, a desiredamount of the raw gas is not adsorbed on the substrate, while the use ofa raw gas-supply time of longer than 10 seconds is not reasonable sinceit is too long from the viewpoint of the throughput. Further, if theflow rate of the raw gas supplied is less than 0.5 sccm, any desiredeffect of adsorption cannot be expected, while the use of a flow rate ofthe raw gas on the order of greater than 200 sccm is not reasonablesince it takes a long period of time for the exhaust treatment after thecompletion of the adsorption step.

After the completion of the adsorption step, the excess raw gas isevacuated out of the apparatus through the gap 106 a and the exhaustpath V (or the exhaust means 113). Then the substrate stages 102 a and102 b are descended to thus open every vacuum chambers and thesubstrate-conveying means 110 is operated to transfer the substrate Sfrom the substrate stage 102 a to the substrate stage 102 b. Then apredetermined or desired pressure (for instance, 2×10⁻⁵ Torr) is againestablished in the vacuum film-forming apparatus 101 including theinteriors of the bell-jar-shaped vacuum containers 104 a and 104 b bythe evacuation, the substrate stage 102 b is ascended so that thesubstrate stage and the bell-jar-shaped container 104 b form a space 105b and that the substrate S is positioned within the space (see FIG. 1(b)). At this stage, it is preferred that the substrate stage 102 a issimultaneously ascended such that the atmosphere within the space 105 athus formed is isolated from that within the space 105 b.

In the state in which the substrate S to be deposited with a film isplaced in the foregoing position, the temperature of the substrate S onthe substrate stage 102 b is maintained at a predetermined level (at atemperature of, for instance, 450° C.) by the heating means, while areactant gas (20 to 1000 sccm) such as excited NH₃ and/or H₂ gas isintroduced into the vacuum chamber through the gas-introduction means107 b in such a manner that the pressure within the space 105 b formedin the vacuum chamber is maintained at a desired level (on the order of,for instance, 5×10⁻¹ Torr) and the reactant gas is allowed to thus reactwith the raw gas adsorbed on the substrate S for a predetermined periodof time (for instance, 0.1 to 10 seconds) to thus form a desired barrierfilm (a layer of, for instance, a ZrB₂ film or a ZrBN film) on thesubstrate S. In this case, the reactant gas introduced is preferablyexcited and converted into radicals by the action of a catalytic means.

In the reaction step or the step for the decomposition of the raw gas,if the supply time of the excited reactant gas is less than 0.1 second,the reaction between them cannot be ensured, while the use of the supplytime of longer than 10 seconds is too long and is not reasonable fromthe viewpoint of the throughput. Further, if the flow rate of thereactant gas supplied is less than 20 sccm, any desired reaction effectcannot be expected, while the use of a flow rate of the reactant gassupplied on the order of greater than 1000 sccm is not reasonable sinceit takes a long period of time for the exhaust treatment after thecompletion of the reaction step.

After the completion of the foregoing reaction step, the gases asby-products as well as the unreacted or unchanged gases are externallyevacuated out of the apparatus through the gap 106 b and the exhaustpath V (or the exhaust means 113). Then the substrate stages 102 a and102 b are brought down to thus open every vacuum chambers and thesubstrate S is again transported to the substrate stage 102 a for theadsorption step by the operation of the substrate-conveying means 110.Then a series of film-forming operations comprising the adsorption andreaction steps is repeated over a desired times according to theforegoing procedures to thus form a thin film (a ZrB₂ film or a ZrBNfilm) having a desired thickness. As a result, it has been confirmedthat the resulting thin film is completely free of the formation of anyoverhang on, for instance, holes and/or trenches and that the film islikewise formed even on the inner wall of these holes and trenches in agood coverage.

As has been discussed above in detail, the spaces 105 a and 105 b areexhausted, during the film-forming process, through the gaps 106 a and106 b each formed during the film-forming process in such a manner thatit surrounds the periphery of the corresponding substrate stage. This isbecause, if the gases present in these spaces are directly dischargedinto the vacuum film-forming apparatus 101 through the gap, the raw gasand the reactant gas are admixed together in the vacuum film-formingapparatus when the foregoing adsorption and reaction steps aresimultaneously carried out and particles are thus formed through thegas-phase reaction of these components. It is preferred for theprevention of the formation of any particle that the apparatus isprovided with an exhaust path V, whereby the bell-jar-shaped containers104 a and 104 b are capped with the exhaust means 113 provided with suchan exhaust path V (see FIGS. 1( b) and 1(c)) when practicing theseadsorption and reaction steps. If the exhaust means 113 is secured toeach substrate stage 102 a, 102 b through fixing members 114 as shown inFIG. 1( c), at least part of the exhaust means can be formed of a pipingwork 115 such as a bellows type one, whereby the exhaust means can inturn be moved in response to the upward and downward movement of thesubstrate stages 102 a and 102 b. The exhaust means or the exhaust pathsmay be so designed that they can be combined into one as shown in theattached figure to thus externally discharge gases out of the vacuumfilm-forming apparatus 101. Alternatively, each vacuum container isprovided with a separate exhaust means so that the exhaust gas mayseparately, externally be discharged from the apparatus.

When it is intended to supply the foregoing excited reactant gas ontothe substrate S to be deposited with a film, it is sufficient that thegas piping work 108 b is connected to the gas-introduction means 107 bthrough a catalyst chamber 202 (FIG. 2) comprising a catalytic meanssuch as a known catalyst wire of, for instance, tungsten and that thereactant gas, which passes through the catalyst chamber and which isthus excited, is supplied onto the surface of the substrate S throughthe gas-introduction means equipped with a shower plate or a dispersionplate. Alternatively, the foregoing catalytic means may be arrangedwithin the space 105 b or at the upstream side of the shower plate orthe dispersion plate of the gas-introduction means 107 b and thereactant gas may thus be excited through the catalytic means before thesupply of the reactant gas to the substrate S through the shower plateor the dispersion plate equipped with a cooling mechanism. In thisrespect, the temperature of the catalyst wire during the film-formingprocess is preferably changed from that observed for the same in thewaiting or standby state by controlling the electric current or electricvoltage applied to the wire.

The temperature control of the tungsten wire can be, for instance,carried out as follows: When the reactant gas is excited by heating thetungsten wire to a temperature of about 1700° C. by the application ofan electric current to the wire, the intensity of the electric currentmay variously vary depending on the pressure around the wire or flowrate of the gas passing through the wire and a constant-current circuituse, but it in general sets at a level of about 12 A for a wire of 0.5mm (diameter). If such an electric current is continuously applied tothe wire, the temperature of the wire increases and this in turn leadsto an increase of the temperature of, for instance, the wafer or thesubstrate stage. Accordingly, the temperature thereof should becontrolled by changing the temperature of the catalyst wire from thefilm-forming step to the waiting or standby stage. When the gas pressurenear the tungsten wire is, for instance, 100 Pa, an electric current of12 A is applied to the wire to thus heat the same to a temperature ofabout 1700° C. during the film-forming process to thus excite thereactant gas, while the temperature of the wire during the standby stateis maintained at a lower level. In this respect, for instance, thetemperature of the wire is found to be 500° C. when a current of 5 A isapplied thereto and 190° C. when a current of 3 A is applied. Thus, theintensity of the electric current to be applied to the wire can beadjusted in response to the temperature of the substrate stage.

According to the foregoing thin film-forming method, as will be clearfrom FIG. 2, H₂ gas and/or NH₃ gas as reactant gases are introduced intothe catalyst chamber 202 through the gas-introduction port 202 a, thereactant gases are thus excited in the catalyst chamber in which thereactant gases are brought into close contact with the catalyst heatedto a temperature generally ranging from 1600 to 1900° C. and preferably1700 to 1800° C., the reactant gases thus excited are then introducedinto the vacuum chamber at a flow rate ranging from 20 to 1000 sccm fora time ranging from 0.1 to 10 seconds by opening the valve 201 so thatthe reactant gases undergo the reaction with the raw gas adsorbed on thesubstrate S (the reaction step). In this connection, if the catalysttemperature is less than 1600° C., the catalyst wire of, for instance,tungsten can never show its catalytic effect sufficiently and H₂ gasand/or NH₃ gas are converted into their radicals in only a lowefficiency, while if the temperature exceeds 1900° C., the catalyst wireof, for instance, tungsten per se undergoes sublimation due to the heatthus generated and this in turn leads to the breakage of the catalystwire and/or the tungsten atoms thus sublimated may serve as contaminantsand thus adversely affect the quality of the resulting thin film. Inthis connection, the apparatus is so designed that the pressure in thecatalyst chamber 202 does not cause any change even when opening orclosing a valve 201 such as an isolation valve dividing the catalystchamber 202 from the vacuum chamber because of the presence of a ventline 207 positioned between the catalyst chamber 202 and the valve 206which is arranged between the catalyst chamber 202 and the exhaust means205.

As discussed above, there has been described an example of the methodfor the preparation of a thin film, in which only one substrate S iscyclically transported between the substrate stages 102 a and 102 b andthe adsorption and reaction steps are repeated over a desired times tothus form a desired thin film. In this respect, the adsorption andreaction steps are separately carried out in the spaces of thepredetermined vacuum chambers. However, it is also possible to form sucha desired thin film as follows: For instance, two arms are fixed to theshaft part 110 a to thus simultaneously transfer two substrates S to bedeposited with thin films between the substrate stages 102 a and 102 bso that a series of operations can simultaneously be carried out. Morespecifically, one of these two substrates is subjected to an adsorptiontreatment, while the other is subjected to a reaction treatment. In thisconnection, at least three of substrates S may simultaneously beprocessed or subjected to adsorption and/or reaction steps whileincreasing the numbers of arms and vacuum chambers to be used.

Moreover, in the thin film-forming method which makes use of the vacuumfilm-forming apparatus 301 as shown in FIGS. 3 to 5, the road-lockchamber 314 and the vacuum film-forming apparatus are first evacuated byoperating the vacuum exhaust means, the first substrate S is thentransferred to the vacuum film-forming apparatus through the road-lockchamber 314 so that the substrate S is placed on a substrate-supportingpart 309 a disposed on the turn table 308 (see FIG. 5( a)). At thisstage, the heating means built in each substrate stage 302 a to 302 d isoperated.

A desired pressure (for instance, 2×10⁻⁵ Torr) is established within thevacuum film-forming apparatus 301 by the foregoing evacuation and theupper face of the turn table 308 is then brought into contact with theopening of each corresponding bell-jar-shaped container 306 a to 306 dby ascending the turn table 308 by the action of a driving shaft 308-2due to the operation of a driving means 308-1 to thus form each desiredvacuum chambers having each spaces 307 a to 307 d. In this respect, theturn table is ascended till the substrate-supporting part 309 a providedthereon with the substrate S is projected into the bell-jar-shapedcontainer 306 a to thus realize a state in which the substrate S ispositioned within the first space 307 a thus formed (see FIG. 5( b)). Atthis stage, all of the openings of the bell-jar-shaped containers arecovered with the turn table 308 so that the atmospheres in the spaces307 a to 307 d are isolated from one another.

Then, when the driving means 303 a to 303 d are operated, thestage-supporting table 305 is elevated by the action of the drivingshafts 304 a to 304 d till the substrate stages 304 a to 304 d areprojected through the corresponding through holes 308 a to 308 d,respectively. Thus the upper face of the substrate stage is pressedagainst the lower face of the substrate S and the upper face of thestage-supporting table is brought into contact with the lower face ofthe turn table by further ascending the stage-supporting table so thatthe substrate S placed on the substrate stage 302 a is in thefilm-forming position within the first space 307 a (see FIG. 5( c)).

Thereafter, in the state as shown in FIG. 5( c), the first substrate Son the substrate stage 302 a is heated to and maintained at a desiredtemperature (ranging from 50 to 450° C., preferably 80 to 300° C., forinstance, 300° C.) by a heating means, then a raw gas such as Zr(BH₄)₄gas is introduced, through the gas-introduction means 311 a, into thespace 307 a within the vacuum chamber formed by the turn table 308 andthe bell-jar-shaped container 306 a at a flow rate ranging from 0.5 to200 sccm so that a desired gas pressure (for instance, 3×10⁻¹ Torr) isestablished within the space and thereafter these conditions aremaintained for a predetermined period of time (for instance, 0.1 to 10seconds, for instance, 2 seconds) to thus adsorb the raw gas on thesurface of the first substrate S. In this case, the gases are dischargedout of the apparatus through the exhaust port 305 a of thestage-supporting table 305 which communicates with the exhaust hole 308e and the exhaust path formed within the stage-supporting table andaccordingly, the pressure within the space 307 a can be maintained at apredetermined level. In addition, after the completion of the adsorptionstep, the excess raw gas is likewise exhausted out of the apparatusthrough the evacuation.

After the completion of the foregoing adsorption step, thestage-supporting table 305 is descended and the turn table 308 islikewise descended to open each vacuum chamber and to thus return theapparatus to the state as shown in FIG. 5( a). Thereafter the turn table308 is rotated by a desired angle (in this embodiment, 90 deg.) so thatthe positions of the substrate stages 302 a to 302 d are in goodagreement with those of the through holes 308 a to 308 d, respectively.In this case, the first substrate S, on which the raw gas has beenadsorbed, is transported to the position just above the second substratestage 302 b and placed on the substrate-supporting part 309 b, while thesecond substrate S is conveyed through the road-lock chamber 314 andplaced on the substrate-supporting part 309 a of the vacant substratestage 302 a previously occupied by the first substrate S.

Then the vacuum film-forming apparatus 301 is evacuated till thepressure of the interior thereof reaches the predetermined levelspecified above, the turn table 308 is elevated so that the upper faceof the turn table comes in contact with the opening of eachbell-jar-shaped container 306 a to 306 d to thus form each correspondingspace 307 a to 307 d. More specifically, the turn table 308 is elevatedtill the substrate-support parts 309 b and 309 a, on which the first andsecond substrates S are placed respectively, are projected into thebell-jar-shaped containers 306 b and 306 a, respectively so that each ofthe substrates S is placed at the desired position in the second space307 b or the first space 307 a thus formed (see FIG. 5( b)). At thisstage, all of the openings of the bell-jar-shaped containers are coveredwith the turn table 308 so that the atmospheres in the spaces 307 a to307 d are isolated from one another.

Then, when the driving means 303 a to 303 d are operated, thestage-supporting table 305 is elevated by the action of the drivingshafts 304 a to 304 d till each substrate stage is projected through thecorresponding through hole 308 a to 308 d of the turn table. Thus theupper face of the substrate stage is pressed against the lower face ofeach substrate S and the upper face of the stage-supporting table isbrought into contact with the lower face of the turn table by furtherascending the stage-supporting table so that the first and secondsubstrates S placed on the substrate stages 302 b and 302 a respectivelyoccupy the corresponding film-forming positions within the respectivesecond and first spaces 307 b and 307 a.

At this stage in which the substrates to be deposited with films are inthe respective film-forming positions, the first substrate S, which isplaced on the substrate stage 302 b and which carries the raw gasadsorbed on the surface thereof, is heated to and maintained at adesired temperature (for instance, 500° C.) and a gas obtained byexciting a reactant gas such as NH₃ gas and/or H₂ gas through theionization or by converting the same into radicals (in a flow rate of,for instance, 20 to 1000 sccm) is introduced into the space 307 b withinthe second vacuum chamber formed by the turn table 308 and thebell-jar-shaped container 306 b through the gas introduction means 311 btill the pressure within the space 307 b reaches a desired level (forinstance, 5×10⁻¹ Torr), followed by the reaction of the excited reactantgas with the raw gas adsorbed on the substrate S while allowing thesystem to stand for a predetermined period of time (in the order of 0.1to 10 seconds, for instance, 2 seconds) to thus form a thin film of, forinstance, ZrB₂ or ZrBN on the first substrate S.

Simultaneously, the second substrate S placed on the substrate stage 302a is heated to and maintained at a desired temperature specified above(for instance, 300° C.) and then a raw gas is introduced into the space307 a within the first vacuum chamber formed by the turn table 308 andthe bell-jar-shaped container 306 a through the gas-introduction means311 a till the pressure in the space 307 a reaches a predetermined level(for instance, 3×10⁻¹ Torr), followed by allowing the system to standfor a predetermined period of time specified above (for instance, 2seconds) so that the raw gas is adsorbed on the surface of the secondsubstrate S.

After the completion of the reaction step for the first substrate S andthe adsorption step for the second substrate S, the excess raw gas,unreacted or unchanged reactant gas, by-product gases or the like areexhausted out of the apparatus through the exhaust holes 308 e, 308 f,the exhaust port 305 a formed on the upper face of the stage-supportingtable 305 and the exhaust path formed within the stage-supporting table,through evacuation. Then the stage-supporting table 305 is brought downand the turn table 308 is likewise descended so that every vacuumchambers are opened. Thereafter the turn table 308 is further rotated bya desired angle (in this embodiment, 90 deg.) so that the positions ofthe substrate stages 302 a to 302 d are in good agreement with those ofthe through holes 308 a to 308 d, respectively. In this case, the firstsubstrate S is transported to the position just above the thirdsubstrate stage 302 c while the second substrate S is transported to theposition just above the second substrate stage 302 b and thesesubstrates S are thus placed on the substrate-supporting parts.Moreover, the third substrate S is transferred through the road-lockchamber 314 and put on the vacant substrate-supporting part of thesubstrate stage 302 a, which has previously been occupied by the secondsubstrate S.

Then the adsorption steps are carried out for the first and thirdsubstrates S and the reaction step is carried out for the secondsubstrate S according to the same procedures used above. After thecompletion of these steps, the excess raw gas, the unchanged reactantgas, the by-product gases or the like are externally exhausted out ofthe film-forming apparatus through the same procedures for theevacuation used above. Thereafter, the stage-supporting table 305 isdescended and the turn table 308 is also descended to open each vacuumchamber. Then the turn table 308 is further rotated by a desired angle(in this embodiment, 90 deg.) so that the positions of the substratestages 302 a to 302 d are in good agreement with those of the throughholes 308 a to 308 d, respectively. In this case, the first substrate Sis transported to the position just above the fourth substrate stage 302d, the second substrate S is transported to the position just above thethird substrate stage 302 c and the third substrate S is transported tothe position just above the second substrate stage 302 b. Morespecifically, these substrates S are thus placed on the correspondingsubstrate-supporting parts. Moreover, the fourth substrate S istransferred through the road-lock chamber 314 and put on the vacantsubstrate-supporting part 309 a of the substrate stage 302 a, which haspreviously been occupied by the third substrate S. Then the adsorptionsteps are carried out for the second and fourth substrates S, while thereaction steps are carried out for the first and third substrates Saccording to the same procedures used above.

Thereafter, in the apparatus in which these four substrates S are put onthe corresponding substrate-supporting parts, the adsorption andreaction steps are repeated over desired times generally ranging fromseveral times to several hundred times, while rotating the turn table bya desired angle at a time to thus form a thin film (for instance, a ZrBNfilm or a ZrB₂ film) having a desired thickness on each substrate S. Inthis connection, it has been confirmed that the resulting thin film iscompletely free of any overhang on the upper portion of, for instance,holes and/or trenches and it is formed even on the inner face of theseholes and trenches in a good coverage.

As has already been described in connection with FIG. 1, when a reactantgas is first excited and then supplied onto the substrate S to bedeposited with a film as has been discussed above, it is sufficient thatthe gas piping work is connected to the gas-introduction means through acatalyst chamber 202 (FIG. 2) comprising a catalytic means such as aknown catalyst wire of, for instance, tungsten and then the excitedreactant gas is supplied onto the surface of the substrate S through thegas-introduction means equipped with a shower plate or a dispersionplate. Alternatively, the foregoing catalytic means may be arrangedwithin the space or at the upstream side of the shower plate or thedispersion plate of the gas-introduction means and the reactant gas maythus be excited through the catalytic means before the supply of thereactant gas to the substrate S through the shower plate or thedispersion plate equipped with a cooling mechanism. In this respect, thetemperature of the catalyst wire such as a tungsten wire can becontrolled by the method already described above.

Regarding the vacuum film-forming apparatus 301 provided with a turntable and shown in FIGS. 3 to 5, each of the adsorption and reactionsteps is conducted only once during the term elapsed after the substrateto be deposited with a film is transferred to the interior of the vacuumchamber and till the next substrate to be deposited with a film isintroduced into a desired vacuum chamber, for making the explanationsimple. However, it is preferred to carry out each of these stepsseveral times during the spare time before the next substrate isintroduced into a desired vacuum chamber. For instance, in the case of aso-called integration apparatus or the vacuum film-forming apparatusaccording to the present invention which permits the practice of notonly the process for forming a thin film such as a barrier film, butalso the processes prior to and subsequent to the thin film-formingprocess, a considerable time may be required for the transportation of asubstrate to be deposited with a film into the film-forming apparatus.Therefore, it would be quite efficient that the turn table is rotatedduring this spare time and the adsorption and reaction steps may berepeated several times for the substrates which have alreadyaccommodated in the vacuum chambers to improve the throughput and tothus make the best use of the spare time.

In this respect, in forming a thin film using the foregoing thinfilm-forming apparatus according to the present invention, if a raw gas(or a reactant gas) remains within each vacuum chamber or thefilm-forming apparatus in a high concentration, a problem arises, suchthat the remaining gas may cause a gas-phase reaction with the reactantgas (or the raw gas) to form particles and to thus cause deposition ofsuch particles on the inner walls of, for instance, the vacuum chamberand/or the film-forming apparatus. For this reason, it is preferred toevacuate the vacuum chamber to a pressure as low as possible or tointroduce an inert gas (such as N₂ or Ar gas) into the same to thusreduce the remaining gas concentration as low as possible.

According to the foregoing thin film-forming method, for instance, aninsulating film such as a P—SiO film, a BPSG film or an HDP-PSG film, aP—SiOC film, or a low dielectric film such as a porous Low-k film isformed on a substrate by the sputtering technique, the CVD technique ora coating method, the resulting insulating or low dielectric film isetched under the usual etching conditions to thus form, for instance,fine holes and/or trenches each having a high aspect ratio and theresulting product can be used as a substrate to be deposited with a thinfilm for forming a thin film such as a barrier film according to the ALDtechnique as has been described above in detail. In this respect, thethin film such as a barrier film can be formed on the substrate withoutcausing the formation of any overhang on the upper portions of, forinstance, the holes and the thin film of high quality can likewise beformed on the inner walls of the holes or the like in a high coverage.As the foregoing substrate, there may be listed, for instance,substrates currently used in the semiconductor devices such as Sisubstrates.

As has been discussed above in detail, the thin film-forming methodwould permit the formation of a thin film consisting of, for instance,ZrB₂ film or a ZrBN film on a substrate to be deposited with a thin filmincluding the inner walls of holes and/or trenches thereof using a rawgas such as Zr(BH₄)₄ gas and a reactant gas such as at least one ofexcited H₂ gas and NH₃ gas.

Regarding the raw gas, the material for the raw gas undergoes thermaldecomposition when the temperature thereof exceeds 60° C. and therefore,the material is first gasified at a temperature of not more than 60° C.and the resulting raw gas is then transported to a desired vacuumchamber. The raw gas thus generated, for instance, using a unit as shownin FIGS. 6( a) to (c) is introduced into a vacuum chamber at a flow rateranging from 0.5 to 200 sccm for a time ranging from 0.1 to 10 seconds.

More specifically, a net 602 having a very small mesh size is disposedwithin a tank 601 heated to and maintained at a temperature of less thanthe melting point (28.7° C.) of Zr(BH₄)₄ as a raw material such as 25°C. (vapor pressure: 16 mmHg), the granular raw material 603 is placed onthe net, an inert gas such as Ar or N₂ as a bubbling gas is fed to thelower portion of the tank 601 through a mass flow controller 604 to thusmake the inert gas flow through the raw material from the lower portionto the upper portion of the net 602, the raw material is thus sublimedby the action of this bubbling, the raw gas thus obtained is introducedinto a vacuum chamber together with the bubbling gas (see FIG. 6( a)) tothus adsorb the raw gas onto the surface of a substrate on which a filmis to be deposited.

Alternatively, granular raw material 603 is sandwiched between two nets602 a and 602 b disposed within and secured to a tank 601 heated to andmaintained at a temperature of less than the melting point (28.7° C.) ofZr(BH₄)₄ as a raw material such as 25° C., an inert gas such as Ar or N₂as a bubbling gas is fed within the tank 601 through a mass flowcontroller 604 to thus make the inert gas flow through the raw materialfrom the net 602 a to the net 602 b, and the raw material 603 is thussublimed by the action of this bubbling, the raw gas thus generated isintroduced into a vacuum chamber together with the bubbling gas (seeFIG. 6( b)) to thus adsorb the raw gas onto the surface of a substrateto be deposited with a film.

Further, the raw gas may likewise be introduced into a desired vacuumchamber according to the following method: a raw material 603′ isintroduced into a tank 601 heated to and maintained at a temperature ofnot less than the melting point of Zr(BH₄)₄ as a raw material, forinstance, about 50° C. (vapor pressure: 55 mmHg), the raw gas thusgasified is introduced into a desired vacuum chamber while directlycontrolling the gas using a mass flow controller 604′ such as a lowpressure-difference mass flow controller (see FIG. 6( c)) and after theintroduction of the raw gas, it is adsorbed onto the surface of asubstrate to be deposited with a film.

In the present invention, it would be desirable that prior to theforegoing adsorption step, the surface of the substrate S to bedeposited with a film should be pre-treated by introducing, into thevacuum chamber, an excited reactant gas such as H₂ gas and/or NH₃ gasexcited by a catalytic means, preferably hydrogen radicals generated byexciting H₂ gas or hydrogen ions and hydrogen radicals obtained byexciting preferably H₂ gas treated in a plasma generator to thusirradiate the substrate with such an excited gas. This allows thepre-treatment of the surface of a metal film and that of an insulatingfilm formed on the substrate or wafer and this accordingly permits thesubstantial improvement in the adhesion between the thin film to beapplied onto the substrate and the insulating film such as an SiO₂ filmas a primary coat.

Incidentally, various apparatuses and tools, which have been used in thefilm-forming method, such as the film-forming apparatus, the vacuumchambers, the catalytic means and the piping works can be cleaned, forinstance, by the introduction of a cleaning gas such as NF₃ into thesemachinery and tools, while establishing desired conditions within thesame.

The vacuum film-forming apparatus of the present invention permits theindependent establishment of process conditions required for theadsorption and reaction processes and the better acceleration of thereaction between a raw gas and the reactant gas to thus give a thin filmhaving excellent quality and the apparatus can be manufactured at a lowcost.

Consequently, the present invention may effectively be used in thefields of electric and electronics such as the field of semiconductor.For instance, the present invention can be applied to the technicalfields of the production of semiconductor integrated circuits, whichinclude the process for forming a thin film such as a primary coatserving as a barrier film when filling fine contact holes, trenches andother similar structures up with a distributing wire material such as Cuand/or Al.

1-11. (canceled)
 12. A vacuum film-forming apparatus characterized inthat the apparatus comprises a turn table for placing and transferring asubstrate and capable of freely moving up and down; a plurality ofvacuum chamber-forming containers which are arranged such that thevacuum chamber-forming containers are opposed to the turn table andwhich can freely move up and down; and a plurality of gas-introductionmeans which are separately connected to every corresponding vacuumchamber-forming containers, wherein the apparatus is so designed that,upon practicing a film-forming process, one of the turn table and thevacuum chamber-forming container is ascended or descended towards theother or both of the turn table and the vacuum chamber-forming containerare simultaneously ascended or descended to thus bring an upper face ofthe turn table and an opening of the vacuum chamber-forming containerinto contact with one another so that a plurality of vacuum chambers canbe formed, each of which is surrounded by a part of the turn table andeach corresponding vacuum chamber-forming container and that a desiredraw gas and/or a reactant gas can be introduced into a space of eachselected vacuum chamber thus formed among the plurality of the samethrough the gas-introduction means to thus carry out either anadsorption step in which the raw gas is adsorbed on a surface of thesubstrate or a reaction step for allowing the adsorbed raw gas to reactwith the reactant gas.
 13. The vacuum film-forming apparatus as setforth in claim 12, wherein the turn table is provided with, on a samecircumference of a circle, a plurality of trough holes the number ofwhich is identical to that of the vacuum chamber-forming containers; amember for supporting each substrate is disposed at a periphery of eachthough hole; and the apparatus is provided with a substrate stage, as ameans for ascending and descending the substrate placed thereon, whichcan freely go up and down and which can pass through the hole.
 14. Thevacuum film-forming apparatus as set forth in claim 12, wherein theapparatus further comprises a plasma generator which is positioned on anexterior of at least one of the vacuum chamber-forming container. 15.The vacuum film-forming apparatus as set forth in claim 13, wherein theapparatus further comprises a plasma generator which is positioned on anexterior of at least one of the vacuum chamber-forming container. 16.The vacuum film-forming apparatus as set forth in claim 12, wherein theapparatus is further provided with a catalytic means which is connectedto the vacuum chamber-forming container for carrying out the reactionstep and placed on an exterior of the film-forming apparatus or withinthe vacuum chamber for carrying out the reaction step so that thereactant gas excited by the catalytic means can be introduced into aspace for carrying out the reaction step.
 17. The vacuum film-formingapparatus as set forth in claim 13, wherein the apparatus is furtherprovided with a catalytic means which is connected to the vacuumchamber-forming container for carrying out the reaction step and placedon an exterior of the film-forming apparatus or within the vacuumchamber for carrying out the reaction step so that the reactant gasexcited by the catalytic means can be introduced into a space forcarrying out the reaction step.
 18. The vacuum film-forming apparatus asset forth in claim 14, wherein the apparatus is further provided with acatalytic means which is connected to the vacuum chamber-formingcontainer for carrying out the reaction step and placed on an exteriorof the film-forming apparatus or within the vacuum chamber for carryingout the reaction step so that the reactant gas excited by the catalyticmeans can be introduced into a space for carrying out the reaction step.19. The vacuum film-forming apparatus as set forth in claim 16, whereinthe catalytic means and the vacuum chamber-forming container forcarrying out the reaction step are equipped with cooling means.
 20. Thevacuum film-forming apparatus as set forth in claim 13, wherein aplurality of exhaust ports are disposed in a vicinity of an externalperiphery of the substrate-supporting member.
 21. The vacuumfilm-forming apparatus as set forth in claim 12, wherein the vacuumchamber-forming container is a bell-jar-shaped one.
 22. The vacuumfilm-forming apparatus as set forth in claim 13, wherein each of theplurality of substrate stages is equipped with a heating means forheating a substrate.
 23. The vacuum film-forming apparatus as set forthin claim 13, wherein the apparatus is further provided with astage-supporting table, in an interior of which is provided with anexhaust passage, for placing the substrate stages.
 24. The vacuumfilm-forming apparatus as set forth in claim 14, wherein the apparatusis further provided with a stage-supporting table, in an interior ofwhich is provided with an exhaust passage, for placing the substratestages.
 25. The vacuum film-forming apparatus as set forth in claim 15,wherein the apparatus is further provided with a stage-supporting table,in an interior of which is provided with an exhaust passage, for placingthe substrate stages.
 26. The vacuum film-forming apparatus as set forthin claim 16, wherein the apparatus is further provided with astage-supporting table, in an interior of which is provided with anexhaust passage, for placing the substrate stages.
 27. The vacuumfilm-forming apparatus as set forth in claim 17, wherein the apparatusis further provided with a stage-supporting table, in an interior ofwhich is provided with an exhaust passage, for placing the substratestages.
 28. The vacuum film-forming apparatus as set forth in claim 18,wherein the apparatus is further provided with a stage-supporting table,in an interior of which is provided with an exhaust passage, for placingthe substrate stages.
 29. The vacuum film-forming apparatus as set forthin claim 20, wherein the apparatus is further provided with astage-supporting table, in an interior of which is provided with anexhaust passage, for placing the substrate stages.